JP2007302859A - NEW TRANSITION METAL COMPLEX CARRIED BY POLYMER USING p-PHOSPHINE GROUP-CONTAINING STYRENE-STYRENE-BASED COPOLYMER AS LIGAND, AND CATALYST COMPRISING THE COMPLEX - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a more practicable metal complex catalyst carried by a polymer, having a simple structure, easily produceable at a low cost and excellent in the points of recovering and reusing properties or the like; and to provide a ligand for a catalyst, suitable for preparing the catalyst. <P>SOLUTION: The metal complex carried by the polymer is obtained by bringing a phosphorus-containing styrene-based copolymer (A) obtained by copolymerizing 25-90 mol% styrene monomer (1a), 1-70 mol% p-phosphine group-containing styrene (2a) and 1-30 mol% divinylbenzene (3a) [with the proviso that the total percentage of monomers (1a), (2a) and (3a) is 100 mol%] into contact with a metal salt or transition metal complex represented by formula (B): M-X<SB>q</SB>L<SB>r</SB>(wherein, M is a transition metal atom such as Pd, or an ion thereof; X is a halogen ion or the like; L is a ligand such as triphenylphosphine; and q and r are each an integer of ≥0), and contains 0.1-20 wt.% transition metal atom or transition metal ion M expressed in terms of the amount of the transition metal. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a novel polymer-supported transition metal complex having a p-phosphine group-containing styrene-styrene copolymer as a ligand and a catalyst comprising the complex. More specifically, the present invention has a simple structure and is easy at low cost. A p-phosphine group-containing styrene-styrene copolymer that can be suitably used as a polymer-supported transition metal complex catalyst that can be used for 10 times or more, preferably several tens of times of repeated use. The present invention relates to a novel polymer-supported transition metal complex as a ligand, a production method thereof, a catalyst comprising the complex, and a method of synthesizing a compound using the catalyst.

  Catalysts are used in many reactions today to efficiently produce target compounds. In particular, many useful reactions such as high selectivity and specificity using a transition metal complex catalyst have been found in recent years.

  However, since the complex catalytic reaction is a homogeneous reaction, it is difficult to separate the catalyst and the product and unreacted raw materials, is not necessarily thermally stable, is sensitive to oxygen, water, etc., and has a long catalyst life. There are problems such as being shorter than a solid catalyst.

  In particular, in order to solve the problem of difficulty in separating the product and the catalyst, a ligand is attached to a water-insoluble or organic solvent-insoluble polymer, and a metal is further coordinated to form a heterogeneous catalyst. Many attempts have been made to form. Among them, a phosphine compound is introduced into a polymer and coordinated with a transition metal to obtain a heterogeneous catalyst.

  Looking at polymer ligands of phosphine compounds, there are many complex structures, and whether a polymer-supported catalyst can be obtained by a simple and simple synthesis method, or whether recovery and reuse of the catalyst can be performed efficiently There are few examples that have been fully examined up to this point.

  Examples of the simplest structure of the polymer ligand include those in which a triphenylphosphine structure is incorporated into a polystyrene skeleton, and this polymer ligand is as common as commercially available. Therefore, many studies on polymer-supported metal complex catalysts having a triphenylphosphine structure have been reported (Non-Patent Documents 1, 2, and 3).

However, since these ligand structures are triphenylphosphine or similar structures, applicable reactions and substrates are limited.
For example, in a polymer-supported complex catalyst supporting palladium, the substrate is limited to a highly reactive iodine body, a long reaction time is required, or the reaction is limited to an easy reaction (Non-patent Document 2). 3).

If a ligand other than triphenylphosphine can be immobilized on the polymer, the selectivity of the reaction will increase and its usefulness will increase.
One example of a ligand other than triphenylphosphine is dicyclohexylphenylphosphine. There are several polymers having this dicyclohexyl (p-vinylphenyl) phosphine structure (Patent Document 1), and those directly incorporated into a polystyrene skeleton are commercially available.

However, there is no example in which these polymers are used as a ligand for the reaction, and in addition, recovery and reuse are fully studied.
Further, as seen in homogeneous transition metal complex catalysts, it is thought that catalytic activity and recovery / reuse can be improved by changing the ligand structure of the polymer-supported metal complex catalyst. In fact, many examples have been reported in which ligands having various structures are supported on polymers (Non-patent Document 4).

However, there are many cases where the structure of the ligand and the polymerization method are complicated, and there are few examples where the recovery and reuse of the catalyst has been sufficiently studied.
As described above, the conventional catalyst has room for further improvement in terms of the simplicity of the ligand structure, the ease of catalyst preparation, the convenience of repeated reuse, and the like. These characteristics are further improved, and the appearance of more practical polymer-supported transition metal complexes has been demanded.

Therefore, the inventors of the present application have made intensive studies and disclosed in Japanese Patent Application Laid-Open No. 2005-281454 (Patent Document 2) a specific styrene-based monomer, diphenyl (p-isopropenylphenyl) phosphine, and, if necessary, divinylbenzene. A phosphorus-containing styrenic copolymer (A) obtained by copolymerization of the above and a specific formula (B): MX _q L _r (M is a group 9 or group 10 transition metal atom or a 1 to 3 valence group). A Group 9 or Group 10 transition metal cation, X represents a halogen ion, L represents a ligand such as triphenylphosphine, and q and r each represents an integer of 0 or more. A polymer-supported transition metal complex obtained by contacting a metal salt or a transition metal complex represented by the transition metal atom or transition metal ion M in a transition metal equivalent amount of 0.1 to 20% by weight, and the complex It has proposed a Ranaru catalyst. This catalyst has a simple structure, can be easily manufactured at low cost, and can withstand repeated use many times. The recovery and reusability is improved by 1.5 to 2 times compared to conventional catalysts. Therefore, it has an advantage that it can be suitably used as a polymer-supported transition metal complex catalyst.

  However, the polymer-supported transition metal complex catalyst described in Patent Document 2 has a long reaction time when a chloro form (Cl form) is used as a raw material (substrate), and is improved in terms of catalyst recovery and reusability. There was room.

In particular, many transition metals contained in the transition metal complex catalyst are expensive, and in the case of industrial use, it is desired in terms of economy to increase the number of times of recovery and reuse.
For this reason, as a result of further research, the molar ratio (P: M) between the phosphorus atom (P) in the polymer-supported transition metal complex catalyst and the “transition metal atom or transition metal ion” (M) is appropriately selected. It has been found that the number of reuses can be greatly increased. A catalyst comprising a polymer-supported transition metal complex having a p-phosphine group-containing styrene-styrene copolymer as a ligand, such as dicyclohexyl (p-vinylphenyl) phosphine-styrene copolymer, is a raw material (substrate). The present invention was completed by finding that it exhibits excellent catalytic activity even in the case where is a Cl body, the reaction proceeds smoothly with a wider range of raw materials, and the reaction time can be shortened. It came to do.
International Publication WO04 / 030816 Pamphlet JP 2005-281454 A Journal of Organic Chemistry, 1981, 46, 2356 Journal of Organic Chemistry, 1985, 50, 3891 Tetrahedron, 2000, 56, 8661 Chemical Reviews, 2002, 102 (Vol. 10), p. 3217

  The present invention is intended to solve the problems associated with the prior art as described above, has a simple structure, can be easily manufactured at low cost, and is repeatedly used ten times or more, preferably several tens of times. It is an object of the present invention to provide a polymer-supported transition metal complex that can be suitably used as a polymer-supported transition metal complex catalyst that can withstand the same, a catalyst thereof, and a catalyst ligand.

As a result of intensive studies to achieve the above object, the present inventors have found the present invention as described below.
That is, the polymer-supported transition metal complex (C) according to the present invention includes a styrene monomer represented by the following formula (1a): 25 to 90 mol%,
P-phosphine group-containing styrene represented by the following formula (2a): 1 to 70 mol%,
Divinylbenzene represented by the following formula (3a): 1 to 30 mol% (however, phosphorus-containing styrene obtained by copolymerizing all monomers ((1a) + (2a) + (3a)) = 100 mol%) A transition metal atom or transition metal ion M in the complex (C), which is obtained by contacting a copolymer (A) with a metal salt or transition metal complex represented by the following formula (B) The conversion amount is 0.1 to 20% by weight.

(In the formula (2a), R represents any one of an alkyl group, a cycloalkyl group, and an aryl group.)
MX _q L _r (B)
(However, in the formula (B), M represents a group 9 or group 10 transition metal atom or a 1-3 valent group 9 or group 10 transition metal cation,
X represents any one of a halogen ion, an acetoxy ion, a nitrate ion, and a cyan ion,
L represents a ligand selected from triphenylphosphine, tributylphosphine, acetonitrile, benzonitrile, and 1,5-cyclooctadiene, and q and r each independently represent an integer of 0 or more. )
The polymer-supported transition metal complex (C) according to the present invention is:
A component unit derived from a styrene monomer represented by the following formula (1): 25 to 90 mol%,
A component unit derived from p-phosphine group-containing styrene represented by the following formula (2): 1 to 70 mol%,
A component unit derived from divinylbenzene represented by the following formula (3): 1 to 30 mol% (however,
The phosphorus-containing styrenic copolymer (A) containing all the component units ((1) + (2) + (3)) = 100 mol%) is converted into a metal salt or transition metal complex ( B) is coordinated,
The transition metal equivalent of the transition metal atom or transition metal ion M in the complex is 0.1 to 20% by weight.

(In the formula (C), the binding order of the component units (1), (2) and (3) is arbitrary, and the number of repeating units k, l and m each independently represents an integer of 1 or more.
R represents any one of an alkyl group, a cycloalkyl group, and an aryl group;
M represents a Group 9 or Group 10 transition metal atom or a 1 to 3 group 9 or 10 transition metal cation,
X represents any one of a halogen ion, an acetoxy ion, a nitrate ion, and a cyan ion,
L represents a ligand selected from triphenylphosphine, tributylphosphine, acetonitrile, benzonitrile, and 1,5-cyclooctadiene;
q and r each independently represent an integer of 0 or more,
d represents an integer of 1 or more. )
In the present invention, p-phosphine group-containing styrene (2a) or a component unit thereof in the monomer mixture for synthesizing the phosphorus-containing styrene copolymer or the phosphorus-containing styrene copolymer (ligand) ( The content of 2) is 10 to 30 mol% (provided that the total monomer units for synthesizing the phosphorus-containing styrene copolymer or the total component units in the phosphorus-containing styrene copolymer = 100 mol%). preferable.

The molar ratio (P: M) of the phosphorus atom (P) in the polymer-supported transition metal complex (C) to the “transition metal atom or transition metal ion” (M) is usually 1: 1 to 20: 1, The ratio is preferably 2: 1 to 15: 1, more preferably 3: 1 to 8: 1, from the viewpoint of catalyst activity, reusability of the catalyst, and the like.

  In the present invention, the content of the divinylbenzene (3a) or its component unit (3) in the monomer mixture or the phosphorus-containing styrene copolymer (ligand) is 2 to 8 mol% (provided that , Total of all monomers or all component units = 100 mol%).

  Moreover, in this invention, it is preferable that the transition metal conversion amount of the said transition metal atom or transition metal cation (M) in a complex (C) is 1-10 weight% in a polymer carrying | support transition metal complex.

In the present invention, the transition metal atom or transition metal cation (M) is preferably palladium or an ion thereof.
The method for producing the polymer-supported transition metal complex (C) according to the present invention includes:
Styrene monomer represented by the above formula (1a): 25 to 90 mol%, p-phosphine group-containing styrene represented by the above formula (2a): 1 to 70 mol%,
Divinylbenzene represented by the above formula (3a): 1 to 30 mol% (provided that phosphorus is formed by copolymerizing all monomers ((1a) + (2a) + (3a)) = 100 mol%) A styrenic copolymer (A);
The above formula _{(B) [M-X q} L r: definition ibid. It is characterized by contacting (acting) a metal salt or a transition metal complex represented by the formula:

  The catalyst for organic synthesis according to the present invention comprises a polymer-supported transition metal complex (C) as described above, for Grignard coupling reaction, for Suzuki-Miyaura reaction, for Heck reaction, for hydrogenation reaction, for oxo It is characterized by being a catalyst for either a method or a hydrosilylation reaction.

The ligand for a polymer-supported catalyst according to the present invention, particularly preferably the ligand for a polymer-supported transition metal complex catalyst,
Styrene monomer represented by the above formula (1a): 25 to 90 mol%,
P-phosphine group-containing styrene represented by the above formula (2a): 1 to 70 mol%,
Divinylbenzene represented by the above formula (3a): 1 to 30 mol% (provided that the phosphorus content is obtained by copolymerizing all monomers ((1a) + (2a) + (3a)) = 100 mol%) It consists of a styrenic copolymer (A).

  The method for producing biphenyls according to the present invention comprises a Grignard cup comprising a halogenated benzene and an arylmagnesium halide in the presence of an organic synthesis catalyst comprising the polymer-supported transition metal complex (C) described above. It is characterized by ring reaction.

  Further, the method for producing biphenyls according to the present invention comprises a halogenated benzene and a phenyl group-containing boronic acid in the presence of an organic synthesis catalyst comprising the polymer-supported transition metal complex (C) described above. It is characterized by causing a Suzuki-Miyaura reaction.

  Moreover, the method for producing an alkyl-alkoxysilane according to the present invention comprises reacting a 1-alkene with a hydrosilane compound in the presence of an organic synthesis catalyst comprising the polymer-supported transition metal complex (C) described above. It is characterized by letting.

According to the present invention, a phosphorus-containing styrene copolymer (A) obtained by copolymerizing the p-phosphine group-containing styrene monomer (2a) with a styrene monomer (styrene derivative) (1a) and a divinylbenzene compound (3a). ) As a ligand, a more practical polymer-supported metal complex catalyst that has a simple structure, can be easily produced at low cost, and is excellent in terms of recovery and reuse, and the catalyst. Catalytic ligands suitable for preparation are provided.

  Moreover, according to this invention, the suitable manufacturing method of the said polymer carrying | support transition metal complex which can produce the above polymer carrying | supporting transition metal complex (C) safely at low cost and efficiently is provided.

  According to the present invention, the complex (C), which is a use of the catalyst comprising the above complex, is repeatedly reused as a catalyst, and 4-methylbiphenyl and other biphenyls, alkyl-mono, di-acids using the catalyst are reused. There is provided a method for synthesizing these compounds so that a compound such as a trialkoxysilane compound can be produced inexpensively, efficiently and safely.

  Hereinafter, according to the present invention, a novel polymer-supported transition metal complex having a phosphorus-containing styrene copolymer as a ligand, a production method thereof, a catalyst comprising the complex, a synthesis method of a compound using the catalyst, and the like This will be specifically described.

[Polymer-supported transition metal complex]
That is, the polymer-supported transition metal complex (C) according to the present invention includes a specific phosphorus-containing styrenic copolymer (A) described in detail below and the following formula (B) [that is, M−X _q L _r ]. A transition metal atom or a transition metal ion M in the complex (C) in the amount of transition metal in the complex (C) of 0.1 to 20% by weight, preferably 1 to 10% by weight.

  The molar ratio (P: M) of the phosphorus atom (P) in the complex (C) and the “transition metal atom or transition metal ion” (M) is usually 1: 1 to 20: 1, preferably 2: 1 to 15: 1, more preferably 3: 1 to 8: 1.

  Transition metal equivalent amount of transition metal atom or transition metal ion M in this complex (C), or molar ratio of phosphorus atom (P) and “transition metal atom or transition metal ion” (M) (P: M) If the amount is less than the above range, the reaction rate of the various reactions using the resulting catalyst tends to decrease, and when the polymer-supported transition metal complex is used as a catalyst, the yield of the target compound tends to decrease.

  This polymer-supported transition metal complex (C) is a bead-like solid and is swellable with respect to these solvents even when the temperature is raised to the boiling point of various solvents (D) as shown below under normal pressure. Is substantially insoluble.

As this insoluble solvent (D), in addition to water,
Aromatic hydrocarbon solvents such as benzene and toluene;
Ethers such as ethyl ether, tetrahydrofuran (THF), dioxane;
Halogenated hydrocarbon solvents such as chloroform and dichloromethane;
Aliphatic alcohols such as methanol, ethanol, butanol;
Amides such as dimethylformamide and dimethylacetamide;
Ketones such as acetone;
Is mentioned.

Hereinafter, the phosphorus-containing styrenic copolymer (A) to be the polymer ligand (A) in the polymer-supported transition metal complex (C), and “metal salt or transition metal complex” in the complex (C) ( The metal salt or transition metal complex (B), which becomes the B) portion, will be described.
<Phosphorus-containing styrene copolymer (A) or polymer ligand (A)>
The polymer ligand (A) in the polymer-supported transition metal complex (C) is a phosphorus-containing styrene copolymer (A) ligand.

The polymer ligand (A) is a styrene monomer represented by the following formula (1a): 25 to 90 mol%, preferably 60 to 80 mol%,
P-phosphine group-containing styrene monomer represented by the following formula (2a): 1 to 70 mol%, preferably 10 to 30 mol%,
Divinylbenzene represented by the following formula (3a): 1 to 30 mol%, preferably 1 to 20 mol%, particularly 2 to 8 mol% (provided that all monomers ((1a) + (2a) + (3a)) = 100 mol%).

(In the formula (2a), R represents any one of an alkyl group, a cycloalkyl group, and an aryl group.)
When R is an alkyl group, it may have about 1 to 10 carbon atoms and may be linear or branched. Specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include alkyl groups such as butyl group, isobutyl group, t-butyl group, amyl group, hexyl group, heptyl group and octyl group.

  When R is a cycloalkyl group, those having about 5 to 7 carbon atoms are exemplified, and specific examples include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  When R is an aryl group, a part of the hydrogen atoms contained may be substituted with the above alkyl group having about 1 to 3 carbon atoms, specifically, for example, a phenyl group, 2-methyl Aryl groups such as phenyl group, 3-methylphenyl group, 4-methylphenyl group and the like can be mentioned.

In this invention, you may use the 1 type (s) or 2 or more types of monomer (2a) which has such various R at the time of copolymerization of (1a), (2a), and (3a).
In the present invention, two Rs in the above formula (2a) may be the same or different from each other, but the same is preferable from the viewpoint of easy availability of raw materials, cost reduction, ease of synthesis, and the like. .

Among the Rs, the cycloalkyl group and the aryl group are desirable from the viewpoint of recovery and reusability of the resulting catalyst.
Specific examples of such a monomer (2a) include dicyclohexyl (p-vinylphenyl) phosphine and diphenyl (p-vinylphenyl) phosphine.

  This phosphorus-containing styrenic copolymer (A) (also referred to as polymer ligand (A)) is a bead-like solid as in the case of the polymer-supported transition metal complex (C). The transition metal complex (C) rises to the boiling points of various solvents (D) as described above under normal pressure, whereas the transition metal complex (C) shows insolubility even when the temperature rises to the boiling point of each solvent. Even if it is heated, it is substantially insoluble even if it shows swelling properties with respect to these solvents.

This polymer ligand (A) has such an arrangement when the amount of each monomer (1a), (2a), (3a) used in the synthesis of the polymer ligand (A) is in the above range. When a Grignard coupling reaction, a Suzuki-Miyaura reaction, or the like is performed using a polymer-supported transition metal complex catalyst (C) having a ligand (A), the catalyst (C) is rapidly released in the solvent as the reaction starts. In the catalyst, gaps are generated in the phosphorus-containing styrenic copolymer (A) site, particularly the polymer chain site, and the degree of freedom of the polymer chain constituting the catalyst is increased. , Its metal salt or transition metal complex (B) site) and substrate (eg:
The chance of contact with a Grignard coupling reaction and the like increases, and the contactability is improved, and the Grignard coupling reaction, the Suzuki-Miyaura reaction, etc. tend to proceed rapidly.

If the amount of the styrene monomer (1a) is less than the above range, it tends to be disadvantageous in terms of economy, and if it is more than the above range, the phosphorus atom content decreases and the effect as a ligand. Tends to decrease.

  Further, when the amount of the monomer (2a), that is, the amount of p-phosphine group-containing styrene (2a) such as dicyclohexyl (p-vinylphenyl) phosphine is less than the above range, the effect as a ligand tends to be reduced. If it exceeds the range, it tends to be disadvantageous in terms of economy.

  When this monomer (3a) is used, if the amount of this monomer (3a), that is, the amount of divinylbenzene (3a) is less than the above range, the strength of the polymer-supported transition metal complex tends to be reduced. When the amount is large, the swelling property of the polymer-supported transition metal complex catalyst in the solvent during the reaction is lowered, and the chance of contact between the catalyst and the substrate is reduced, and the reactivity tends to be lowered.

  In such a phosphorus-containing styrene copolymer (A), each component unit derived from each monomer (1a), (2a), (3a) (component units (1), (2), (3 )) May be arranged at random, or may be arranged in blocks.

  The two vinyl groups of divinylbenzene (3a) can be bonded to the o, m, and p positions of the benzene ring, but those bonded to the m and p positions are usually readily available, especially at the m and p positions. A mixture of bonded divinylbenzene is easily available at a low cost, and if such divinylbenzene (3a) or the like is copolymerized with the other monomers (1a) and (2a), the desired performance is finally obtained. A polymer-supported transition metal complex or the like is obtained.

  The structure of such a phosphorus-containing styrene copolymer (A) can be determined by using an infrared absorption spectrum (IR), a nuclear magnetic resonance spectrum (NMR), or the like.

Moreover, the content of phosphorus (P) in the phosphorus-containing styrenic copolymer (A) to be a polymer ligand can be determined by the method described later.
<Metal salt or transition metal complex (B)>
MX _q L _r (B)
In the formula (B), M represents a group 9 or group 10 transition metal atom, or a 1-3 valent group 9 or group 10 transition metal cation.

  Examples of group 9 transition metals include cobalt (Co), rhodium (Rh), iridium (Ir), etc. Examples of group 10 transition metals include nickel (Ni), palladium (Pd), and platinum. (Pt) etc. are mentioned, Among them, those of Group 9 such as rhodium and cobalt, and those of Group 10 such as palladium and nickel are preferable.

X represents any one of a halogen ion, an acetoxy ion, a nitrate ion, and a cyan ion. Among them, a halogen ion such as F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ , an acetoxy ion, and the like are easily available. This is preferable.

  L represents a ligand selected from triphenylphosphine, tributylphosphine, acetonitrile, benzonitrile, and 1,5-cyclooctadiene, and is limited to these as long as coordination exchange is possible. is not. q and r each independently represent an integer of 0 or more.

As such a metal salt or transition metal complex (B), specifically, for example, a palladium complex represented by dichlorobis (triphenylphosphine) palladium (II), dichloro (1,5-cyclopentadiene) palladium, chloride Examples thereof include palladium, palladium acetate, rhodium chloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, and dichlorobis (triphenylphosphine) palladium (II) and palladium chloride are preferable. These metal salts or transition metal complexes (B) may be used alone or in combination of two or more.
<Contact>
In the polymer-supported transition metal complex (C) of the present invention, the phosphorus-containing styrenic copolymer (A) and the metal salt or transition metal complex (B) are contacted and coordinated, and thus It is presumed that the polymer-supported transition metal complex according to the present invention has a structure represented by the following formula (C).

(The definition of each symbol in (C) will be described later.)
In addition, in the phosphorus-containing styrenic copolymer (A) ligand in the polymer-supported transition metal complex (C), the order in which the component units (1), (2), and (3) are included is arbitrary. These may be arranged at random or may be arranged by forming a block. The number of repeating units k, l, and m each independently represents an integer of 1 or more.

  In the polymer-supported transition metal complex (C) of the present invention, as shown in the above formula (C), the metal salt or transition metal complex (B) is arranged on the phosphorus-containing styrene copolymer (A) used. It has a coordinated structure, and the transition metal equivalent of the transition metal atom or transition metal ion M in the complex (C) is 0.1 to 20% by weight, preferably 1 to 10% by weight.

  In the present invention, the molar ratio (P: M) between the phosphorus atom (P) in the polymer-supported transition metal complex (C) and the “transition metal atom or transition metal ion” (M) is the complex obtained. Considering that the number of times the catalyst is reused remarkably increases, that is, it is possible to effectively use expensive Pd or the like as a raw material, it is usually 1: 1 to 20: 1, preferably 2: 1 to 15: 1. Preferably it is 3: 1-8: 1.

  Such an effect (the point that the number of reuses of the resulting complex catalyst is remarkably increased) is remarkable when R in the polymer-supported transition metal complex (C) is the cycloalkyl group (eg, cyclohexyl group). However, the present invention is not limited to such an embodiment, and even when the R is the aryl group (eg, phenyl group), if the molar ratio is (P: M), a considerably excellent effect can be obtained.

  In addition, when this R is the said alkyl group, this alkyl group is easy to receive oxidation, Therefore The frequency | count of reuse of the obtained complex catalyst is the case where R is the above two (cycloalkyl group, aryl group) It may be slightly lower than

  In order to set the transition metal equivalent amount of M in the complex (C) or the molar ratio (P: M) to the above range, the polymer ligand and the transition metal salt or transition metal complex (B) at the time of preparing the complex It can be adjusted by changing the charging ratio.

  In the phosphorus-containing styrene copolymer (A) (or polymer ligand (A)), each component unit (1), (2), (3) is the same as each of the above-described monomers ( 1a), (2a), (3a) is present in an amount corresponding to the amount.

That is, the phosphorus-containing styrenic copolymer (A) contains the component unit (1) derived from the monomer (1a) in an amount of 25 to 90 mol%, preferably 60 to 80 mol%,
The component unit derived from p-phosphine group-containing styrene (2a) represented by the following formula (2) is contained in an amount of 1 to 70 mol%, preferably 10 to 30 mol%.

  Moreover, the component unit derived from divinylbenzene (3a) represented by the following formula (3) is 1 to 30 mol%, preferably 1 to 20 mol%, particularly 2 to 8 mol% (however, all component units) ((1) + (2) + (3)) = 100 mol%).

In the formula (C), the bonding order of the component units (1), (2), and (3) is arbitrary.
In the component unit (3), two phenylene groups (benzene rings) are sandwiched.

Linked / bonded site represented by {namely, the site of (3-1) and (3-2) in component unit (3)}:

Therefore, the component unit (3) is present in the copolymer and contributes to the crosslinking reaction. However, at any of these bonding sites, the component unit (3) is the other component unit (1), It is combined with either (2) or (3).

  Two linked / bonded sites (3-1) and (3-2) existing across the benzene ring in the component unit (3), that is,

Is present in the o, m, p position, preferably in the m position or p position, corresponding to the type of monomer (3a) used.
The number of repeating units k, m, and l for each component unit independently represents an integer of 1 or more.

The ratio of k, m, and l in the copolymer corresponds to the ratio of the amounts of the monomers (1a), (2a), and (3a) used.
R in the copolymer is the same as that in the monomer (2a).

Other symbols M, X, L, q, and r are the same as in the case of the above formula (B).
d represents an integer of 1 or more.
In the present invention, as described above, the ratio (molar ratio) between the phosphorus atom and the transition metal atom in the polymer-supported transition metal complex (C) is usually 1: 1 to 20: 1, preferably 2: 1. It is desirable that it is ˜15: 1, more preferably 3: 1 to 8: 1 from the viewpoint of excellent catalytic activity, reusability of the catalyst, and the like.

  As an example of the polymer-supported transition metal complex (C), a compound having a molar ratio of phosphorus to palladium (P / Pd) of 2/1 (molar ratio) is represented by the following formula (C-1). Here, phosphorus (P) coordinated to palladium (Pd) may be in the same polymer chain or between different polymer chains.

The structure of such a polymer-supported transition metal complex (C) can be determined by utilizing NMR, ICP analysis, IR (KBr tablet method) and the like.
[Production of polymer-supported transition metal complex (C)]
In the present invention, the polymer-supported transition metal complex (C) is produced by bringing the phosphorus-containing styrene copolymer (A) into contact with the metal salt or the transition metal complex (B). be able to.
<Synthesis of phosphorus-containing styrenic copolymer (A)>
First, in order to obtain a phosphorus-containing styrene copolymer (A), the styrene monomer (1a) which is the copolymerization monomer, the p-phosphine group-containing styrene (2a), and the divinylbenzene (3a). These are used in amounts as described above, and are usually copolymerized in the presence of a polymerization initiator, a solvent and the like.

  In this copolymerization, the amount of the styrene monomer (1a) is 25 to 90 mol%, preferably 60 to 80 mol%, and the monomer (2a) is 1 to 70 mol%, preferably 10 to 30 mol%. It is desirable to use the divinylbenzene monomer (3a) in an amount of 1 mol%, preferably 1 to 20 mol%, preferably 1 to 20 mol%, particularly preferably 2 to 8 mol%. However, all the monomers ((1a) + (2a) + (3a)) = 100 mol%.

If the amount of the styrene monomer (1a) is less than the above range, there is a tendency to be disadvantageous in terms of economy, and if it is more than the above range, the effect as a ligand tends to be reduced.
If the amount of this monomer (2a), that is, the amount of p-phosphine group-containing styrene (2a) is less than the above range, the effect as a ligand tends to be reduced, and if it exceeds the above range, it is disadvantageous in terms of economy. Tend.

  If the amount of the monomer (3a), that is, the amount of divinylbenzene (3a) is less than the above range, the polymer strength tends to be lowered. If the amount is more than the above range, various amounts using the resulting polymer-supported transition metal complex catalyst (C) are used. In the reaction of, for example, Grignard coupling reaction, Suzuki-Miyaura reaction, Heck reaction, hydrogenation reaction, reaction by oxo method, hydrosilylation reaction, etc., the swelling property of the catalyst (particularly the polymer site) is reduced, There is a tendency for the reactivity to decrease due to a decrease in the contact between the catalyst and the substrate (the above-mentioned raw materials for each reaction).

In synthesizing the phosphorus-containing styrene copolymer (A), the following polymerization initiator, solvent and the like are usually used.
Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile (AIBN), azobiscyclohexylcarbonitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), t -Butylperoxybenzoate, di-t-butylperoxide, 1,1-bis (t-butylperoxybenzoate, peroxides such as benzoyl peroxide, etc., preferably AIBN, azobiscyclohexylcarbonitrile, An azo compound such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) is used, and these polymerization initiators are conventionally known polymerization initiators for producing olefinic (co) polymers. For example, in an amount of about 0.5 to 5 parts by weight per 100 parts by weight of the total amount of monomers.

Moreover, as a solvent used if necessary, water;
Aromatic hydrocarbon solvents such as benzene, toluene, xylene;
hydrocarbon solvents such as n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane;
Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride;
Alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol;
Nitrile solvents such as acetonitrile and propionitrile;
Examples include ether solvents such as tetrahydrofuran, 1,4-dioxane, ethyl ether, n-butyl ether, methyl t-butyl ether, and mixed solvents thereof.

When the solvent is used, it is used in an amount of, for example, about 100 to 500 parts by weight per 100 parts by weight of the total amount of monomers.
If necessary, polyvinyl alcohol, methylcellulose, gelatin, polyacrylate, etc. may be added as stabilizers in an amount of about 0.01 to 30 parts by weight per 100 parts by weight of the total amount of monomers.

In the present invention, when the monomers (1a), (2a) and (3a) are copolymerized, they may be heated, pressurized, etc., but the conditions differ depending on the type of monomer, monomer composition ratio, etc. .

For example, the above styrene monomer (1a), dicyclohexyl (p-vinylphenyl) phosphine (2a), which is a kind of p-phosphine group-containing styrene, and divinylbenzene (3a) are combined in the above monomer amount ratio. In the case of polymerization, the reaction may be performed under normal pressure at a reaction temperature of 20 to 100 ° C., preferably 30 to 80 ° C., and for a reaction time of about 3 to 24 hours.

The phosphorus-containing styrenic copolymer (A1) in which the component unit composition thus obtained is a styrene unit / dicyclohexyl (p-vinylphenyl) phosphine (2a) unit / divinylbenzene (3a) unit is used at normal temperature. Under pressure, usually solid.
<Contact of Phosphorus-Containing Styrene Copolymer (A) with Metal Salt or Transition Metal Complex (B) and Obtained Catalyst (C)>
Next, in the present invention, the above-mentioned phosphorus-containing styrenic copolymer (A) and the “metal salt or transition metal complex” (B) are brought into contact (action) to form a polymer-supported transition useful as a catalyst for organic synthesis. The metal complex (C) is manufactured.

  That is, the polymer (A) is coordinated to a transition metal compound (B) having a group 9 or group 10 transition metal atom or a 1 to 3 group 9 or 10 group transition metal cation, and the like. A complex catalyst (C) is obtained. Examples of the transition metal used here include palladium, nickel, rhodium, and platinum.

The preparation method of the catalyst (C) is as follows if one example is given.
The catalyst (C) is prepared by ligand exchange between the phosphorus-containing polymer (A) and a palladium complex represented by, for example, dichlorobis (triphenylphosphine) palladium or dichloro (1,5-cyclopentadiene) palladium. Is done. It can also be prepared directly from palladium chloride and phosphorus-containing polymer (A).

  Since the valence of the metal when acting as a catalyst changes as needed by repeated redox during the reaction, it is considered that the number of coordinated phosphorus also changes accordingly. Therefore, the molar ratio (P / Pd) of phosphorus and metal (eg, Pd) contained in the polymer (A) is difficult to determine uniquely, and may be selected within a range in which the catalytic activity is effective.

  In the case of the present invention, the molar ratio (P / Pd) of phosphorus (P) and metal (M) (example: Pd) contained in the polymer (A) is selected in the range of 1/1 to 20/1. However, it is preferably 2/1 to 15/1, more preferably 3/1 to 8/1.

In addition, the molar ratio (P / M) of phosphorus contained in the polymer (A) and the metal (M) varies depending on the type of complex, and is appropriately selected depending on the metal species.
Contact (reaction) of the copolymer (A) with the metal salt or transition metal complex (B) is carried out, for example, in a THF solvent at 60 to 65 ° C. for 5 to 24 hours under reflux conditions.

The polymer-supported transition metal complex catalyst (C) according to the present invention is useful as a catalyst for organic synthesis and comprises the polymer-supported transition metal complex (C) described above.
This polymer-supported transition metal complex (C) is used as a catalyst for Grignard coupling reaction, Suzuki-Miyaura reaction, and Heck reaction, more than 10 times, depending on use conditions, and more than 30 times. After completion, this expensive noble metal catalyst can be easily separated and recovered from the reaction system at a high recovery rate and reused many times, which is particularly excellent in terms of economy.

  Further, a catalyst comprising a polymer-supported transition metal complex having a dicyclohexyl (p-vinylphenyl) phosphine-styrene copolymer as a ligand has excellent catalytic activity even when the raw material (substrate) is a chloro form. The reaction proceeds smoothly with respect to a wider range of raw materials, and the reaction time can be shortened.

Moreover, from the viewpoint of synthesis of the target product, the purity of the target product can be increased, and a synthesis reaction advantageous in terms of separation and purification can be provided.
In addition, the structure of the ligand (A) is simple, the polymerization method can be easily synthesized using a known method, and the catalyst (C) can be easily prepared at low cost.

[Synthesis Method of Compound Using the Catalyst]
<Synthesis of biphenyls by Grignard reaction>
In the method for producing biphenyls (c) according to the present invention, in the presence of an organic synthesis catalyst (polymer-supported transition metal complex catalyst (C)) comprising the polymer-supported transition metal complex (C) described above. In general, the halogenated benzene (a) such as bromobenzene and the arylmagnesium halide (b) such as p-tolylmagnesium chloride are theoretically equimolar ratios, usually with respect to 1 mole of the halogenated benzene (a). The arylmagnesium halide (b) is subjected to a Grignard coupling reaction in an amount of 0.8 to 2.0 mol, preferably an excess amount of (b), that is, a molar ratio: (b) / (b)> 1. . In this Grignard coupling reaction, a solvent may be used, and heating may be performed if necessary.

Solvents that can normally be used in the synthesis of biphenyls by the Grignard coupling reaction may be any solvent that can coexist with the Grignard reagent. Specific examples include diethyl ether, di-normal butyl ether, methyl tertiary butyl ether, tetrahydrofuran, and the like. Ether solvents such as 1,4-dioxane;
Aromatic hydrocarbon solvents such as benzene, toluene, xylene;
Hydrocarbon solvents such as normal hexane and normal heptane;
Or these mixed solvents are mentioned.

These solvents can be used alone or in combination of two or more.
In the present invention, among these solvents, tetrahydrofuran, toluene, and a mixed solvent thereof are preferable.

  The amount of the catalyst comprising the polymer-supported transition metal complex (C) of the present invention is 100 moles of halogenated benzene such as bromobenzene (a) or arylmagnesium halide such as p-tolylmagnesium chloride (b) as a reaction raw material. % Is 0.0001 to 20 mol%, preferably 0.001 to 2 mol%.

The reaction temperature is selected between room temperature and the reflux temperature of the solvent, but is preferably 40 to 80 ° C.
Since the polymer-supported transition metal complex catalyst (C) of the present invention used in the above reaction is insoluble in water and organic solvents, it is separated from the product and recovered by a simple operation such as decantation or filtration after the reaction. be able to.

  The recovered polymer-supported transition metal complex catalyst (C) has almost no decrease in activity and can be used repeatedly many times (eg, 15 to 20 times), and is suitable for the above-mentioned Grignard coupling reaction at a low cost. It is.

For example, a polymer-supported metal prepared by using diphenyl (p-vinylphenyl) phosphine as the phosphine monomer (2a) and preparing a synthesized copolymer (A) with a ratio of phosphorus to Pd (P / Pd) of 4 When 1 mol% of Pd is used with respect to bromobenzene (a) as a catalyst using complex catalyst (C), Grignard coupling reaction of bromobenzene (a) and p-tolylmagnesium chloride (b) is performed. When repeated, the reaction time was within 5 hours, and the raw material (i) disappeared as the reaction proceeded, and 4-methylbiphenyl (c) was obtained in high yield. (Note that the raw material (b) is usually used in a slightly excessive amount, so it decreases but does not disappear.)
Furthermore, even when the collection and reuse were repeated, the activity of the polymer-supported transition metal complex catalyst (C) was hardly reduced. The catalyst (C) used for this can be repeatedly recovered and used at a recovery rate of 93 to 100%, and the yield of the target compound during this period can maintain a high yield of 80% or more.

The polymer-supported metal complex catalyst (C ′) prepared by adjusting the molar ratio of phosphorus P and Pd (P / Pd) = 1.7 at the time of manufacturing the polymer-supported transition metal complex catalyst (C) was used as the Grignard. When 1 mol% of Pd was used as a catalyst for the coupling reaction, the activity decreased after repeated use only 3-4 times.

In addition, when the polymer-supported transition metal complex catalyst (C) is manufactured, the polymer-supported metal complex catalyst (C ″) prepared by adjusting the molar ratio of phosphorus P to Pd (P / Pd) = 20 is used as the Grignard coupling. When 1 mol% of Pd was used as the reaction catalyst, it took 10 hours or more to complete the reaction.

The catalyst (C) of the present invention, or the catalysts (C ′) and (C ″) is used as Suzuki-Miy.
The same tendency was observed when used for aura reaction and Heck reaction.
Moreover, the rhodium complex (Rh catalyst) of the present invention can be prepared using the ligand for a polymer-supported catalyst of the present invention, and can be used for a hydrogenation reaction and a hydrosilylation reaction.

As described above, the polymer-supported metal complex catalyst according to the present invention has almost the same catalytic activity as that of the corresponding homogeneous catalyst, and an effect superior to that of the conventional catalyst is obtained in terms of recovery and reusability.
<Suzuki-Miyaura reaction>
In the method for producing biphenyls according to the present invention, a halogenated benzene and a phenyl group-containing boronic acid are added in the presence of an organic synthesis catalyst comprising the polymer-supported transition metal complex (C) described above. Suzuki-Miyaura reaction is carried out.

For example, p-bromoacetophenone (formula: CH ₃ —C (O)) as halogenated benzene
-Ph-Br; Ph is a benzene ring) and 1 mol of phenylboronic acid (Ph-B (OH) ₂ ; Ph is a benzene ring) is theoretically equimolar, usually 0.8 to 1. Used in an amount of 5 mol, 1.2 to 3.0 mol of potassium carbonate as a base, and the above polymer-supported transition metal complex catalyst (C) (Pd content 2 to 10%) to 100 mol% of halogenated benzene. On the other hand, in an amount of 0.001 to 2.0 mol% (calculation method will be described later), the solvent THF is used in an amount of 3 to 10 times the total amount of raw materials, and water is used in an amount of 3 to 10 times the amount of the solvent ( Example: THF) At 60-65 ° C., which is the reflux temperature (depending on the reaction temperature, target compound, raw material, amount of base, conditions, etc.), the target compound is reacted for about 0.5-5 hours. Biphenyls such as 4-acetylbiphenyl are obtained. The catalyst (C) used for this can be repeatedly recovered and used at a recovery rate of 90 to 100%, and the yield of the target compound during this period can be maintained at a high yield of about 92 to 99%.

The calculation method of the addition amount (mol%) of the polymer-supported transition metal complex catalyst (C) is “{weight of polymer catalyst (g) × Pd content (%) / atomic weight of Pd (106.42)} / According to “moles of halogenated benzene”.
[Example]
Next, although an Example and a comparative example are described about the polymer carrying | support metal complex catalyst etc. which concern on this invention, this invention is not limited at all by these Examples.
[Example 1-1]
<Synthesis of polymer ligand>
In a 100 ml beaker, 13.5 g (0.13 mol) of styrene, 2.4 g (0.01 mol) of 55% divinylbenzene, 17.3 g of diphenyl (4-vinylphenyl) phosphine (purity 99%, 0.06 mol) ) And 1.0 g (0.005 mol) of azobisisobutyronitrile was added to obtain a uniform solution (a ′).

7 g of gelatin was dissolved in 140 ml of water, mixed with the previous solution (a ′), placed in a 300 ml four-necked flask, and heated to 80 ° C. The mixture was further stirred at the same temperature for 8 hours, cooled to room temperature, and filtered using a glass filter.

  It was washed twice each with water, acetone and THF (tetrahydrofuran) and dried at 60 ° C. for 15 hours to obtain 30.4 g of a polymer ligand which is a phosphorus-containing styrene copolymer.

A large excess of benzyl chloride was allowed to act on the resulting polymer ligand, followed by quaternization and analysis by the Forhardt method. As a result, the phosphorus concentration in the polymer was 1.76 mmol / g.
[Example 1-2]
<Synthesis of polymer ligand>
In a 100 ml beaker, 8.5 g (0.08 mol) of styrene, 0.7 g (0.003 mol) of 55% divinylbenzene, 31.5 g of dicyclohexyl (p-vinylphenyl) phosphine (purity 35%, 0.04 mol) ) And 1.0 g (0.03 mol) of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added to obtain a homogeneous solution (a).

  3.2 g of gelatin was dissolved in 80 ml of water, mixed with the previous solution (a), placed in a 300 ml four-necked flask, and heated to 40 ° C. The mixture was further stirred at the same temperature for 8 hours, cooled to room temperature, and filtered using a glass filter.

  It was washed twice each with water, acetone and THF (tetrahydrofuran) and dried at 60 ° C. for 15 hours to obtain 33.6 g of a polymer ligand which is a phosphorus-containing styrene copolymer.

As a result of analyzing the obtained polymer ligand by the phosphorus content analysis method described below, the phosphorus concentration in the polymer was 0.86 mmol / g.
Analysis of phosphorus content :
<Creation of indicator>
0.12 g of ammonium vanadate was dissolved in 40 ml of warm water, 2 ml of 70% perchloric acid was added, and the volume was adjusted to 50 ml with water (solution A).

2.5 g of ammonium molybdate was dissolved in water and the volume was adjusted to 50 ml (solution B).
<Creation of calibration curve>
Using potassium dihydrogen phosphate (MW 136.09, phosphorus content: 22.76% by weight), several types of solutions having different phosphorus concentrations were prepared ((b)).

5 ml of the above solution (b) and two types of indicators (A solution and B solution) were added to a 50 ml volumetric flask, and the volume was adjusted with water (phosphorus concentration 2 to 20 μg / ml, sample b ′).
Next, the sample (b ′) obtained was allowed to stand for 30 minutes or more (specifically, 60 minutes), and then the absorbance of the sample at 420 nm was measured (measuring device: U-2000 type spectrophotometer, Hitachi, Ltd.). Manufactured by Seisakusho).

A calibration curve was prepared from the absorbance.
<Preparation of sample>
The sample was precisely weighed in a 100 ml Erlenmeyer flask so that the phosphorus content in the sample (phosphorus-containing styrene copolymer) was within the range of the calibration curve.

Concentrated nitric acid (5 ml) and 70% perchloric acid (5 ml) were added to the sample phosphorus-containing styrenic copolymer, and ignited on an electric heater until white smoke appeared (temperature at this time: 143 ° C.).
I continued to ignite for 1 minute after the white smoke came out. After completion of ignition, the mixture was cooled to room temperature (27 ° C.).

The above operation (that is, the operation of adding 5 ml of concentrated nitric acid and 5 ml of 70% perchloric acid to the sample to cooling to room temperature) was repeated until there was no solid component in the solution.
After cooling to room temperature (27 ° C.), 10 ml of water was added to the system and ignited on an electric heater until white smoke appeared. I continued to ignite for 1 minute after the white smoke came out. After completion of ignition, the mixture was cooled to room temperature. This operation was performed once again.

The resulting solution (decomposed solution) was placed in a 50 ml volumetric flask and the volume was adjusted.
5 ml of this solution was taken into a 50 ml volumetric flask, 2 ml of indicator (namely, liquid A and liquid B) was added by 5 ml each, 3 ml of 70% perchloric acid was added, and the volume was adjusted with water.

After standing for 30 minutes or more (specifically, 60 minutes), the absorbance at 420 nm was measured, and the phosphorus content was calculated from the calibration curve.
[Example 2-1]
<Preparation of polymer-supported palladium catalyst>
To a 50 ml beaker, 0.58 g (3.3 mmol) of palladium chloride and 4 ml of concentrated hydrochloric acid were added to dissolve the palladium chloride, followed by filtration. The filtrate was diluted with 100 ml of ethanol and 100 ml of THF, put into a 300 ml four-necked flask, and the polymer obtained in Example 1-1: 7.52 g of a phosphorus-containing styrene copolymer (13.2 mmol as phosphorus contained in the polymer). Was added and reacted at reflux temperature for 8 hours.

  After cooling, it was filtered and washed twice with THF. It was dried at 60 ° C. for 15 hours to obtain 7.8 g of a polymer-supported palladium catalyst. The obtained polymer (polymer-supported palladium catalyst) was subjected to ICP analysis (manufactured by Seiko Instruments Inc., inductively coupled plasma emission spectrometer, model number: SPS1700HVR). As a result, the Pd content was 4.1% by weight. From this result, the ratio (molar ratio) of phosphorus and palladium in the obtained polymer-supported palladium catalyst was as follows.

Phosphorus: 7.52 × 1.76 = 13.2 mmol,
Palladium: 7.8 × 0.041 × 1000 / 106.42 = 3.0 mmol,
Phosphorus / palladium (molar ratio) = 13.2 / 3.0 = 4.4 / 1.0 = 4.4,
It became.
[Example 2-2]
<Preparation of polymer-supported palladium catalyst>
To a 50 ml beaker, 0.58 g (3.3 mmol) of palladium chloride and 4 ml of concentrated hydrochloric acid were added to dissolve the palladium chloride, followed by filtration. The filtrate was diluted with 100 ml of ethanol and 100 ml of THF, put into a 300 ml four-necked flask, and the polymer obtained in Example 1-2: 15.34 g of a phosphorus-containing styrene copolymer (13.2 mmol as phosphorus contained in the polymer). Was added and reacted at reflux temperature for 8 hours.

After cooling, it was filtered and washed twice with THF. It was dried at 60 ° C. for 15 hours to obtain 15.7 g of a polymer-supported palladium catalyst.
The obtained polymer (polymer-supported palladium catalyst) was subjected to ICP analysis (manufactured by Seiko Instruments Inc., inductively coupled plasma emission spectrometer, model number: SPS1700HVR). As a result, the Pd content was 2.2% by weight.

From this result, the ratio (molar ratio) of phosphorus and palladium in the obtained polymer-supported palladium catalyst was as follows.
Phosphorus: 15.34 × 0.86 = 13.2 mmol,
Palladium: 15.7 × 0.022 × 1000 / 106.42 = 3.2 mmol,
Phosphorus / palladium (molar ratio) = 13.2 / 3.2 = 4.1 / 1.0 = 4.1,
It became.
[Example 3-1]
<Grignard coupling reaction>
Bromobenzene 4.0 g (25 mmol), 1.7 mol / kg p-tolyl magnesium chloride THF solution 20 g (34 mmol as p-tolyl magnesium chloride) in a 200 ml capacity four-necked flask, polymer obtained in Example 2-1 0.5 g of supported palladium catalyst (Pd content: 4.1%) (1 mol% with respect to 100 mol% of bromobenzene) and 30 ml of toluene were added and reacted at reflux temperature. The reaction was followed by gas chromatography until the starting bromobenzene disappeared.

The number of moles of the polymer-supported Pd catalyst was calculated by “weight of polymer-supported Pd catalyst (g) × Pd content (%) / atomic weight of Pd (106.42)”. The mol% of the polymer-supported palladium catalyst is a value (%) obtained by dividing the number of moles by the number of moles of bromobenzene.

  The yield of 4-methylbiphenyl as the target compound was calculated from the value obtained by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). However, it was 91%.

  After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with 20% sulfuric acid and THF, respectively, and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 99%). ).

The recovered catalyst was repeatedly used, but even if it was repeatedly used 10 times, the raw material bromobenzene disappeared within 3 hours.
Thus, the reaction time (h), yield (%), and recovery rate during the repeated use of the catalyst for the synthesis of 4-methylbiphenyl are shown together in Table 1-1.

  The reaction time is the time until the raw material bromobenzene disappears, and the yield is a value calculated from the purity of the product (by area percentage method) determined by gas chromatography, and the recovery rate is The value (%) is obtained by dividing the recovered catalyst amount by the catalyst use amount before use.

  Confirmation that 4-methylbiphenyl was produced was confirmed by comparing the retention times of the gas chromatography of the product (reaction solution) with the standard product manufactured by Tokyo Chemical Industry Co., Ltd. .

[Example 3-2]
<Grignard coupling reaction>
Bromobenzene 4.0 g (25 mmol), 1.7 mol / kg p-tolylmagnesium chloride THF solution 20 g (34 mmol as p-tolylmagnesium chloride) in a 200 ml capacity 4-neck flask, polymer obtained in Example 2-2 1.2 g of supported palladium catalyst (Pd content 2.2%) (1 mol% with respect to 100 mol% of bromobenzene) and 30 ml of toluene were added and reacted at reflux temperature. The reaction was followed by gas chromatography until the starting bromobenzene disappeared.

The number of moles of the polymer-supported Pd catalyst was calculated by “weight of polymer-supported Pd catalyst (g) × Pd content (%) / atomic weight of Pd (106.42)”. The mol% of the polymer-supported palladium catalyst is a value (%) obtained by dividing the number of moles by the number of moles of bromobenzene.

  The yield of 4-methylbiphenyl as the target compound was calculated from the value obtained by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). However, it was 92%.

  After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with 20% sulfuric acid and THF, respectively, and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 99%). ).

The recovered catalyst was repeatedly used, but even if it was used 20 times, the raw material bromobenzene disappeared within 5 hours.
The reaction time (h), yield (%), and recovery rate during the repeated use of the catalyst for the synthesis of 4-methylbiphenyl are summarized in Table 1-2.

  The reaction time is the time until the raw material bromobenzene disappears, and the yield is a value calculated from the purity of the product (by area percentage method) determined by gas chromatography, and the recovery rate is The value (%) is obtained by dividing the recovered catalyst amount by the catalyst use amount before use.

  Confirmation that 4-methylbiphenyl was produced was confirmed by comparing the retention times of the gas chromatography of the product (reaction solution) with the standard product manufactured by Tokyo Chemical Industry Co., Ltd. .

[Example 4-1]
<Suzuki-Miyaura reaction>
In a 100 ml four-necked flask, 4.0 g (20 mmol) of p-bromoacetophenone, 3.7 g (30 mmol) of phenylboronic acid, 5.5 g (40 mmol) of potassium carbonate, and the polymer-supported palladium catalyst obtained in Example 2-1 ( 0.4 g (Pd content: 4.1%) (0.8 mol% with respect to 100 mol% of p-bromoacetophenone), 20 ml of water and 20 ml of THF were added, and the mixture was reacted at reflux temperature. The reaction was followed by gas chromatography until the starting p-bromoacetophenone disappeared.

  The yield of the target compound, 4-acetylbiphenyl, was calculated from the value obtained by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). However, it was 95%.

  After completion of the reaction, the mixture was filtered using a glass filter, and the filtered catalyst was washed twice with 20% sulfuric acid and THF, respectively, and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 100%). ).

Although the recovered catalyst was repeatedly used, the raw material p-bromoacetophenone disappeared within 3 hours even after repeated use.
The reaction time (h), yield (%), and catalyst recovery rate (%) during the use of the catalyst repeatedly in the synthesis of 4-acetylbiphenyl are shown in Table 2-1.

  In addition, confirmation that 4-acetyl biphenyl which is the target compound was produced was made by comparing the retention time of the gas chromatography of the product (reaction solution) with the standard product manufactured by Tokyo Chemical Industry Co., Ltd. Formation of biphenyl was confirmed.

  The definitions of reaction time, yield and recovery rate are the same as in Example 3-1.

[Example 4-2]
<Suzuki-Miyaura reaction>
In a 100 ml four-necked flask, 4.0 g (20 mmol) of p-bromoacetophenone, 3.7 g (30 mmol) of phenylboronic acid, 5.5 g (40 mmol) of potassium carbonate, the polymer-supported palladium catalyst obtained in Example 2-2 ( Pd content 2.2%) 0.8 g (0.8 mol% with respect to 100 mol% of p-bromoacetophenone), 20 ml of water, and 20 ml of THF were added and reacted at reflux temperature. The reaction was followed by gas chromatography until the starting p-bromoacetophenone disappeared.

  The yield of the target compound, 4-acetylbiphenyl, was calculated from the value obtained by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). However, it was 97%.

  After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with 20% sulfuric acid and THF, respectively, and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 99%). ).

Although the recovered catalyst was repeatedly used for the synthesis of 4-acetylbiphenyl, the raw material p-bromoacetophenone disappeared within 3 hours even after repeated use 30 times.
The reaction time (h), yield (%), and catalyst recovery rate (%) during the use of the catalyst repeatedly in the synthesis of 4-acetylbiphenyl are summarized in Table 2-2.

In addition, confirmation that 4-acetyl biphenyl which is the target compound was produced was made by comparing the retention time of the gas chromatography of the product (reaction solution) with the standard product manufactured by Tokyo Chemical Industry Co., Ltd. Formation of biphenyl was confirmed.

  The definitions of reaction time, yield and recovery rate are the same as above.

[Example 4-3]
(Suzuki-Miyaura reaction)
In a 100 ml four-necked flask, 3.1 g (20 mmol) of p-chloroacetophenone, 3.7 g (30 mmol) of phenylboronic acid, 5.5 g (40 mmol) of potassium carbonate, and the polymer-supported palladium catalyst obtained in Example 2-2 ( Pd content 2.2%) 0.8 g (0.8 mol% with respect to 100 mol% of p-chloroacetophenone), 20 ml of water and 20 ml of THF were added and reacted at reflux temperature. The reaction was followed by gas chromatography until the starting p-chloroacetophenone disappeared.

  The yield of the target compound, 4-acetylbiphenyl, was 95% when the purity (area percentage method) of the product was determined by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B) and calculated from this. It became.

  After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with 20% sulfuric acid and THF, respectively, and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 99%). ).

Although the recovered catalyst was repeatedly used, the raw material p-chloroacetophenone disappeared within 2 hours even after repeated use.
Thus, Table 2-3 summarizes the reaction time (h), yield (%), and catalyst recovery rate (%) during which the catalyst was used repeatedly for the synthesis of the target compound 4-acetylbiphenyl. .

  The definitions of reaction time (h), yield (%), and recovery rate (%) are the same as above.

[Example 5-1]
<Heck reaction>
In a 100 ml four-necked flask, 4.0 g (20 mmol) of p-bromoacetophenone, 2.6 g (30 mmol) of methyl acrylate, 2.3 g (23 mmol) of potassium acetate, and the polymer-supported palladium catalyst obtained in Example 2-1 ( 0.2 g of Pd content (4.1%) (0.4 mol% with respect to 100 mol% of p-bromoacetophenone) and 30 ml of N, N-dimethylacetamide were added and reacted at 90 to 100 ° C. The reaction was followed by gas chromatography until the starting p-bromoacetophenone disappeared.

  The yield of methyl 3- (4-acetylphenyl) acrylate was determined by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). The calculated value was 90%.

After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with THF and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 99%).
The recovered catalyst was repeatedly used, but the starting material p-bromoacetophenone disappeared within 5 hours even after repeated use.

  Thus, the reaction time (h), yield (%), and catalyst recovery rate (%) during the use of the catalyst repeatedly in the synthesis of methyl 3- (4-acetylphenyl) acrylate are summarized in Table 3- It is shown in 1.

The definitions of reaction time, yield and recovery rate are the same as above.
The confirmation that the target compound, methyl 3- (4-acetylphenyl) acrylate, was produced was that the reaction solution was analyzed by GC-MS and the molecular ion peak was 204 (molecular weight of the target compound). ,confirmed.

[Example 5-2]
<Heck reaction>
In a 100 ml four-necked flask, 4.0 g (20 mmol) of p-bromoacetophenone, 2.6 g (30 mmol) of methyl acrylate, 2.3 g (23 mmol) of potassium acetate, and the polymer-supported palladium catalyst obtained in Example 2-2 ( 0.2 g (Pd content 2.2% with respect to 100 mol of p-bromoacetophenone) 0.2 g (0.3 mol% with respect to 100 mol% of p-bromoacetophenone) and 30 ml of N, N-dimethylacetamide were added and reacted at 90-100 ° C. I let you. The reaction was followed by gas chromatography until the starting p-bromoacetophenone disappeared.

  The yield of methyl 3- (4-acetylphenyl) acrylate was determined by measuring the purity (area percentage method) of the product by gas chromatography (manufactured by Shimadzu Corporation, model number: GC-14B). The calculated value was 93%.

After completion of the reaction, the mixture was filtered using a glass filter, and the catalyst separated by filtration was washed twice with THF and dried at 60 ° C. for 15 hours to recover the catalyst (recovery rate 98%).
Although the recovered catalyst was repeatedly used, the raw material p-bromoacetophenone disappeared within 5 hours even after repeated use.

  Thus, the reaction time (h), yield (%), and catalyst recovery rate (%) during the use of the catalyst repeatedly in the synthesis of methyl 3- (4-acetylphenyl) acrylate are summarized in Table 3- It is shown in 2.

  The confirmation that the target compound, methyl 3- (4-acetylphenyl) acrylate, was produced was that the reaction solution was analyzed by GC-MS and the molecular ion peak was 204 (molecular weight of the target compound). ,confirmed.

  The definitions of reaction time, yield and recovery rate are the same as above.

[Comparative Example 1-1]
The same operation as in Example 2-1 was performed to obtain a polymer-supported palladium complex with P / Pd = 1.7.

Using the obtained polymer-supported palladium complex, the reaction was carried out in the same manner as in Example 3-1.
After the reaction, the catalyst was recovered and repeatedly used. It took 8 hours or more for the raw material to disappear after 5 uses.

In the case of Example 3-1, the raw material disappeared within 3 hours even when the catalyst was repeatedly used 10 times or more.
The reaction time, yield, and recovery rate during this period are summarized in Table 4-1.

  The definitions of reaction time, yield and recovery rate are the same as above.

[Comparative Example 1-2]
The same operation as in Example 2-2 was performed to obtain a polymer-supported palladium complex with P / Pd = 1.6.

Reaction was carried out in the same manner as in Example 3-2 using the obtained polymer-supported palladium complex.
After the reaction, the catalyst was recovered and repeatedly used. It took 10 hours or more for the raw material to disappear after 15 uses.

In the case of Example 3-2, the raw material disappeared within 5 hours even when the catalyst was repeatedly used 20 times or more.
The reaction time, yield, and recovery rate during this period are summarized in Table 4-2.

  The definitions of reaction time, yield and recovery rate are the same as above.

[Comparative Example 2-1]
The same operation as in Example 2-1 was performed to obtain a polymer-supported palladium complex with P / Pd = 20.3.

Using the obtained polymer-supported palladium complex, the reaction was carried out in the same manner as in Example 3-1.
However, the reaction was not completed over 10 hours.
[Industrial applicability]
The polymer ligand of the present invention can be easily synthesized because of its simple structure and polymerization method. In addition, polymer-supported metal complex catalysts prepared using these ligands, such as polymer-supported transition metal complexes including polymer-supported palladium catalysts used in Suzuki-Miyaura reaction, Grignard coupling reaction, Heck reaction, etc. Since the catalyst can be easily removed and recovered from the reaction system, it is highly useful in terms of separation and purification.

Further, since an expensive noble metal catalyst can be recovered and reused, it is a useful method from the viewpoint of economy.
In particular, the polymer ligand of the present invention is less deteriorated due to use than a normal styrene polymer, and the number of times of reuse of a polymer-supported metal complex catalyst prepared using the polymer ligand can be greatly increased. Very useful in synthesis reactions.

Claims (11)

Styrene monomer represented by the following formula (1a): 25 to 90 mol%,
P-phosphine group-containing styrene monomer represented by the following formula (2a): 1 to 70 mol%,
Divinylbenzene represented by the following formula (3a): 1 to 30 mol% (however, phosphorus-containing styrene obtained by copolymerizing all monomers ((1a) + (2a) + (3a)) = 100 mol%) The system copolymer (A) is brought into contact with the metal salt or transition metal complex represented by the following formula (B), and the transition metal equivalent of the transition metal atom or transition metal ion M is 0.1-20. Polymer-supported transition metal complex in weight percent.

(In the formula (2a), R represents any one of an alkyl group, a cycloalkyl group, and an aryl group.)
MX _q L _r (B)
(However, in the formula (B), M represents a group 9 or group 10 transition metal atom or a 1-3 valent group 9 or group 10 transition metal cation,
X represents any one of a halogen ion, an acetoxy ion, a nitrate ion, and a cyan ion,
L represents a ligand selected from triphenylphosphine, tributylphosphine, acetonitrile, benzonitrile, and 1,5-cyclooctadiene, and q and r each independently represent an integer of 0 or more. ) A component unit derived from a styrene monomer represented by the following formula (1): 25 to 90 mol%,
A component unit derived from p-phosphine group-containing styrene represented by the following formula (2): 1 to 70 mol%,
Component unit derived from divinylbenzene represented by the following formula (3): 1 to 30 mol% (however, all component units ((1) + (2) + (3)) = 100 mol%) The metal salt or transition metal complex (B) represented by the formula (B) in claim 1 is coordinated to the containing styrene copolymer (A) at the phosphorus atom site,
The polymer-supported transition metal complex (C) represented by the formula (C), wherein the transition metal equivalent of the transition metal atom or transition metal ion M is 0.1 to 20% by weight.

(In the formula (C), the binding order of the component units (1), (2) and (3) is arbitrary, and the number of repeating units k, l and m each independently represents an integer of 1 or more.
R represents any one of an alkyl group, a cycloalkyl group, and an aryl group;
M represents a Group 9 or Group 10 transition metal atom or a 1 to 3 group 9 or 10 transition metal cation,
X represents any one of a halogen ion, an acetoxy ion, a nitrate ion, and a cyan ion,
L represents a ligand selected from triphenylphosphine, tributylphosphine, acetonitrile, benzonitrile, and 1,5-cyclooctadiene;
q and r each independently represent an integer of 0 or more, and d represents an integer of 1 or more. ) Content of said p-phosphine group containing styrene (2a) or its component unit (2) is 10
3 to 30 mol% (provided that all monomers for synthesizing the phosphorus-containing styrenic copolymer or total component units in the phosphorus-containing styrenic copolymer = 100 mol%). The polymer-supported transition metal complex as described.   The content of the divinylbenzene (3a) or its component unit (3) is 2 to 8 mol% (provided that all the monomer units for synthesizing the phosphorus-containing styrene copolymer or all the component units in the phosphorus-containing styrene copolymer) The polymer-supported transition metal complex according to any one of claims 1 to 3, wherein the total is 100 mol%.   The molar ratio (P: M) between the phosphorus atom (P) and the transition metal atom or transition metal ion (M) in the polymer-supported transition metal complex (C) is 2: 1 to 15: 1. The polymer-supported transition metal complex according to any one of 1 to 4. The molar ratio (P: M) between the phosphorus atom (P) and the transition metal atom or transition metal ion (M) in the polymer-supported transition metal complex (C) is 3: 1 to 8: 1. The polymer-supported transition metal complex according to any one of 1 to 4.   The polymer-supported transition according to any one of claims 1 to 6, wherein the transition metal equivalent amount of the transition metal atom or the transition metal cation (M) is 1 to 10% by weight in the polymer-supported transition metal complex (C). Metal complex.   The polymer-supported transition metal complex according to any one of claims 1 to 7, wherein the transition metal atom or the transition metal cation (M) is palladium or an ion thereof. Styrene monomer represented by formula (1a) of claim 1: 25 to 90 mol%,
P-phosphine group-containing styrene represented by the formula (2a) of claim 1: 1 to 70 mol%
When,
Divinylbenzene represented by formula (3a) of claim 1 is copolymerized with 1 to 30 mol% (however, all monomers ((1a) + (2a) + (3a)) = 100 mol%) A phosphorus-containing styrenic copolymer (A),
The method for producing a polymer-supported transition metal complex according to any one of claims 1 to 8, wherein the metal salt or transition metal complex represented by formula (B) of claim 1 is contacted.   A Grignard coupling reaction, a Suzuki-Miyaura reaction, a Heck reaction, a hydrogenation reaction, an oxo method, and a hydrosilylation reaction comprising the polymer-supported transition metal complex according to any one of claims 1 to 8. Any of these catalysts for organic synthesis. Styrene monomer represented by the following formula (1a): 25 to 90 mol%,
P-phosphine group-containing styrene represented by the following formula (2a): 1 to 70 mol%,
Divinylbenzene represented by the following formula (3a): 1 to 30 mol% (however, phosphorus-containing styrene obtained by copolymerizing all monomers ((1a) + (2a) + (3a)) = 100 mol%) A ligand for a polymer-supported catalyst comprising a copolymer (A).

(In the formula (2a), R represents any one of an alkyl group, a cycloalkyl group, and an aryl group.)